Will Samuel has been named as the chairman of TSB by the board of Lloyds Banking Group.
Samuel, who is currently chairman at the Ecclesiastical Insurance Group and Howden Joinery Group, will oversee TSB's network of 631 branches, which Lloyds plans to list on the London Stock Exchange later in 2014.
"Will brings a wealth of experience to the role and is well-regarded by the market and across the financial services industry. He is a key hire and will be instrumental in building TSB's independent future as a challenger to the other high street banks," said Lloyds chairman Win Bischoff.
Samuel is a City veteran and was previously a director of Schroders, a vice-chairman of investment banking at Citigroup Europe, a senior adviser at Lazard and a senior adviser to the Prudential Regulatory Authority.
He joins TSB at a time when Lloyds bank recently boosted its annual banker bonus pool by 10% to £395m ($658.4m, €480.7m) after the financial more than doubled its underlying profit to £6.2bn.
Lloyds chief António Horta-Osório and his right-hand man confirmed that the group is planning to sell TSB shares this summer as executives are well-prepared for the sale.
According to a statement by Horta-Osório, Lloyds is ready to sell TSB shares from the summer of 2014 onwards and is "ready to do whatever the government wants to do" on the sale.
"It is pretty well advanced. The prospectus is well in hand and progressing well," added finance director George Culmer.
Lloyds revealed only a week ago that it plans a £1.5bn float of TSB after the government sold a 6% shareholding in the bank to financial institutions in September 2013.
Lloyds is 33% owned by the government and its largest investor is the UKFI. It has to get permission from the government before it can start paying shareholders a dividend. The last time Lloyds paid a dividend was in 2008.